Limestone Wet Scrubbing of Sulfur Dioxide from Power Generation

13 Limestone Wet Scrubbing of Sulfur Dioxide from Power Generation Flue Gas for High and Low Sulfur Fuels

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ROBERT

J. G L E A S O N

Research-Cottrell, Inc., P.O. Box 750, Bound Brook, N.J. 08805 FRANK

HEACOCK

Arizona Public Service, Phoenix, Ariz.

Limestone wet scrubbing is considered the most viable process approach for sulfur dioxide emission control on coal-fired power generation boilers. Systems under development have been concerned primarily with operational reliability. Sulfur dioxide absorption efficiency has been given secondary treatment. Pilot plant studies on high and low sulfur fuels using packed tower absorbers have shown the inlet SO concentration and slurry composition as significant factors in the removal efficiency and operational reliability. Mass-transfer coefficients have been developed for a wetted film packing. Variable height packed absorbers can provide high absorption efficiency for both high and low sulfur fuels. Hence, compliance with State and Federal regulations can be achieved in the extreme low sulfur coal conditions. 2

'"phe Environmental Protection Agency (EPA) through the Clean Air Act of 1967 and its amendments of 1970 has established the primary and secondary ambient air quality standards for sulfur dioxide and other pollutants. These standards were used to guide the State governments in developing their regional implementation programs (1). The primary air quality standards protect the public health while the secondary standards concern the national welfare (property, environment, etc.). A

Background Codes. The annual average short-term sulfur dioxide concentrations established for the air quality standards are given in Table I. Sulfur oxide 152 Jimeson and Spindt; Pollution Control and Energy Needs Advances in Chemistry; American Chemical Society: Washington, DC, 1974.

13.

GLEASON AND HE ACOCK

153

Limestone Wet Scrubbing

concentrations at 0.03 and 0.02 ppm are the primary and secondary annual standards, respectively. To avoid short-term unhealthy or unsatisfactory conditions, the sulfur oxide must not exceed 0.1-0.14 ppm for more than one 24 hr period per year. To achieve these standards, EPA has proposed emission codes for new and modified industrial plants that are emitting sulfur oxides. For fossil-fired steam generators contracted for construction or modifications after August 17, 1971, the Federally mandated emission standards are 1.2 lbs S0 /MMBtu for coal-fired and 0.8 lb S 0 / M M B t u for oil-fired generators. In Table II, these standard codes are also expressed in outlet concentrations, 620 ppm coal and 440 ppm oil.


2

Table I. r p

2

National Ambient Air Quality Standards for Sulfur Oxides .

Primary

Secondary

Averaging

ng/M*

ppm

pg/M

ppm

Annual 24 hr 3 hr

80 360

0.03 0.14

60 260 1300

0.02 0.1 0.5

Table II.

3

Standards for Sulfur Dioxide Emissions, New and Retrofit Abatement Systems (2)

Fuel Coal Oil

Emission Std lbs S0 /MMBtu

}

2

1.2 0.80

Approx. Flue Outlet S0 Concn, ppm (dry) 2

620° 440

° Assuming 15% excess air and no preheater leakage.

The State implementation programs for sulfur dioxide and other pollutants were submitted after January 1972 for EPA approval or rejection by May 1972. Each program plan was to achieve primary and secondary standards. EPA has also recommended uniform pollution abatement for each region within the specific States; however, this recommendation has created some uncertainty and confusion (2). The electric utilities industries have found it difficult to anticipate the regional codes being adopted by the States or the acceptability of the plans by EPA. For example, this could require a coal-fired station burning low sulfur fuel to reduce the emissions to less than 150 ppm if 70 to 90% removal is adopted; however, a plant in the same region burning high sulfur fuel could be emitting as much as 400 ppm and achieving the same removal efficiency. Even today the emission codes in many regions are still controversial. Industrial plants burning low sulfur fuels could be unfairly equated with high sulfur

Jimeson and Spindt; Pollution Control and Energy Needs Advances in Chemistry; American Chemical Society: Washington, DC, 1974.


154

POLLUTION CONTROL AND ENERGY NEEDS

fuel users on a percentage abatement basis where both are required to control the emissions. Lime and Limestone Wet Scrubbing. The problem of atmospheric pollution by sulfur oxides has been given extensive attention by research and development firms in recent years and several process types are being proposed for full scale application. Lime and limestone wet scrubbing appears to be the most promising approach for immediate application. The major difficulty with the limestone or lime systems is solid deposition in the absorption device which could create unreliability and unscheduled shutdowns for the power plant. In general, the power industry desires the following of a scrubbing device in a flue gas-cleaning system: operational reliability, a minimum of four-to-one turndown ratio, low pressure drop characteristics, high absorption efficiency potential, good alkali utilization, acceptable mist elimination, and future process adaptability. Wet Scrubbing in Packed Towers. The packed absorption tower has been considered and used in lime and limestone scrubbing of S 0 . It has demonstrated its capabilities in most of the previously listed characteristics. However, commercially available packings have difficulty maintaining a reliable operation with calcium-based wet scrubbing because of scale deposition. In England as early as 1930 and again in the 1950s an open grid-type packing was used for scrubbing S 0 with limestone. The grids were constructed from wood strips or slats that allowed high liquid-to-gas ratio and low pressure drop. The absorber was tested over a period of years with minimal process difficulty. Over 3,500 hr of operation have been reported with scale-free conditions (3). Presently, Research-Cottrell has developed a modern wetted film packing similar in many respects to the wood grid tower. The wetted film packing is constructed from corrugated sheets of neoprene-impregnated asbestos or several plastic types. The packing has high specific surface, low pressure, and high liquid rate capabilities. Tests on both high and low sulfur fuels have been successful. Controlled scaling has been reported under both fuel conditions. Longevity tests lasting three weeks on low sulfur coal have shown that little deposition takes place within the absorption device. 2

2

Process Description The system used in conjunction with the tower is illustrated in Figure 1. Flue gas containing S 0 andflyash enters the FDS (S-l) where it is contacted concurrently with a limestone slurry which removes most of theflyash and a fraction of the S0 . The combined stream is then sent 2

2


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CLEASON AND HE ACOCK

155



to the cyclonic mist eliminator (TW-1) where the slurry is separated from the gas. From the mist eliminator, the flue gas flows through the packed absorber section where it is contacted countercurrently with another limestone slurry stream. A significant portion of the remaining SO2 is removed here. The tower absorber section is separated from the cyclonic mist eliminator by a plate containing a conical hat. This arrangement allows the flue gas to leave the cyclonic mist eliminator but prevents the slurry leaving the packed absorption tower from combining with the slurry stream leaving the FDS. Hence, most of the fly ash entering the system is isolated from the absorption tower and is confined to the FDS slurry stream. EXIT GAS •j STACK -TO REHEATER MAKE-UP WATER TW-I PACKED TOWER

F-l

I

MAKE-UP

I

WATER

1

TK-I FDS SLURRY TANK

Figure 1.

FEEDER

•

TK-2 TOWER TANK

Processflowdiagram

Limestone is fed to the system through a variable-speed feeder (F-l) which is mounted on top of the tower slurry tank (TK-2). Slurry from this tank is pumped to the absorber section of the tower where it is contacted countercurrently with the flue gas. The reacted slurry then flows by gravity back to the primary tower slurry tank. An agitator mounted on top of the tank maintains a uniform slurry suspension. To prevent the buildup of reaction products, a small stream is bled from the tower slurry tank (TK-2) and sent to the FDS slurry tank (TK-1). Limestone slurry, which also contains fly ash, is pumped from the FDS slurry tank to the FDS (S-l) where it is contacted with the incoming


156


flue gas. The combined stream of slurry and gas is separated in the cyclonic mist eliminator, and the slurry stream is cycled back to the FDS slurry tank. An agitator mounted on top of the tank maintains a uniform solids distribution. Results and Discussion Transfer Coefficient Calculations. The mass-transfer coefficients were calculated with the relationship developed by Chilton and Colburn (4): NQ Downloaded by CORNELL UNIV on October 26, 2016 | http://pubs.acs.org Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch013

0

Y = Nqq = K = a = P = Z = G =

= -In (1-7)

(1)

K a P Z G

(2)

absorption efficiency, fraction number of overall gas-phase transfer units overall mass-transfer coefficients, lb-mole/hr-ft -atm surface area per unit volume of packing, ft /ft total pressure of the system, atm height of tower, ft gasflowrate, lb-mole/hr-ft . 2

2

3

2

One assumes in using the above equation that the liquid is well mixed vertically, the chemical reaction is irreversible, the sulfur dioxide back pressure is negligible, and the interfacial area per unit of liquid volume is constant throughout the tower. Table III. Mass-Transfer Coefficients for Low Sulfur Coal (0.5% Sulfur or 400 ppm)"

Material

Specific Area, ft /ft*

Packing Ht, ft

Limestone Stoichiometry, % Theor.

Neoprene-coated Neoprene-coated Neoprene-coated Polypropylene Neoprene-coated

43 43 68 68 43

5 2 5 4 5

77 97 85 100 91

1

MassTransfer Coejf., Ib-Mole/hr (ft )-atm 0.31 1.07 0.96 1.26 1.09

2

L / G = liquid-to-gas ratio, 50-55 gal per 1000 f t P = 0.865 atm limestone grind = 90%-200 mesh 8

a

Mass-transfer coefficients calculated from average absorption efficiency. More than 10 measurements were averaged for each coefficient value.


13.

GLEASON AND HEACOCK


1-6 T

0 +

60

1

1

1

1

1

1

1

1

I

1

1

70

80

90

100

110

LIMESTONE

Figure 2.

157


»

ST0ICH10Jft£TRJ£_FJEED. tm

Mass-transfer coefficients for low sulfur fuels (0.3% sulfur)

Low Sulfur Coal. In a pilot system sponsored by the Arizona Public Service, absorption tests with several types of Munters wetted film packing were performed using limestone as an alkali reagent. A high surface area packing, 68 ftVft3, and a low surface area packing, 43 ftVft8, were tested at several tower heights. Operating conditions were set at levels suitable for a stable and reliable process. High mass-transfer coefficients were measured at packing heights between 2 and 5 ft. Limestone stoichiometric feed was varied from 77 to 100%. The calculated mass transfer coefficients and the operating conditions are given in Table III. Transfer coefficients between 0.31 and 1.26 were computed for the limestone stoichiometric range. The absorption efficiency follows almost directly the limestone feed rate as illustrated in Figure 2.


158


Absorption measurements with 0.2N sodium hydroxide solution and operating conditions approximately the same as for the low sulfur limestone tests gave a mass-transfer coefficient of 1.18 lb-mole/hr-fV-atm (5). This compares closely with the values measured with C a C 0 at 100% stoichiometric feed. For sodium hydroxide/sulfur dioxide absorption, the liquid phase resistance can be considered negligible. This suggests that the limestone/S0 system at low sulfur coal conditions falls within a gas phase-resistant process. By selecting a tower height and a limestone feed, one could set the absorption efficiency at a level suitable for the emission codes. High Sulfur Coal. Mass-transfer coefficients for high sulfur coal did not follow any simple pattern. Absorption efficiency varied with inlet S 0 concentration, limestone stoichiometry, and limestone grind. For a sulfur dioxide concentration at 1000 ppm, the stoichiometry had a significant effect on the mass transfer. Limestone stoichiometry below 100% gave poor absorption; above 100%, the mass-transfer coefficient varied between 0.38 and 0.84 lb-mole/hr-ft -atm for limestone feeds between 100 and 140%, respectively (see Table IV). At higher levels of sulfur dioxide (1600 ppm), the calculated coefficients decrease sharply (6). The mass-transfer measurements at 100-140% stoichiometry gave values from 0.35 to 0.38 lb-mole/hr-ft -atm. At this higher S 0 level, stoichiometry had little effect, indicating a significant liquid phase mass-transfer resistance. 3


2

2

2

2

2

Table IV. Mass-Transfer Coefficients with High Limestone Scrubbing Limestone Stoichiometry j

S0 Inlet Concn, ppm 2

%

1000 1000 1000 1600 1600 1600

100 120 140 100 120 140

Sulfur

Coal -

Mass-Transfer" Coeff., lb-Mole/hr-ft -atm 2

0.385 0.510 0.843 0.252 0.308 0.385

-Packing = 68 ft'/ft Height = 5 ft G = 70 lb-mole/hr-ft* P = 1.0 atm Limestone grind = 75%-200 mesh L / G = 45 gal per 1000 ft . 3

3

This insensitivity to limestone feed is illustrated in Figure 3. At 1000 ppm, the S 0 absorption is more than doubled as the limestone feed is increased from 100 to 140%, while at 1600 ppm the same limestone increase improved the absorption by approximately 50%. 2


13.

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159


0.9

0.8

0.7

o CO od

^0.6

CO Downloaded by CORNELL UNIV on October 26, 2016 | http://pubs.acs.org Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch013

UJ

CO

0.5

-J

0.4

O 0.3

0.2

90

100

110

LIMESTONE

Figure 3.

Table V .

120

130

140

STOICHIOMETRY, •/•

Mass-transfer coefficients of high sulfur dioxide concentrations

Mass-Transfer Coefficients with Limestone Mesh Size Variation

S0 Inlet Concn, ppm

Limestone Grind, %-mesh

Mass-Transfer* Coeff. lbs-mole/hr-fP-atm

1300 1300 1300

89-325 75-200 60-200

0.665 0.366 0.287

2

}

'Packing = 68 f t /f t Height = 5 ft G = 70 lb-mole/hr-ft P = 1.0 atm Limestone stoichiometry = 115%. 2

s

2

Influence of Limestone Particle Size. The liquid phase resistance with limestone alkali is expected for the process conditions normally experienced with high sulfur coal. The solubility of C a C 0 is much lower 3


160


than demanded by flue gas containing above 1000 ppm, even at very high liquid flows through the absorbers (above 50 gal per 1000 ft ). Consequently, the controlling resistance would be the dissolution. To determine the sensitivity of the dissolution rate, three limestone grind sizes were tested at similar process conditions. Material ground to 60%-200 mesh, 75%-200 mesh, and 89%-325 mesh gave coefficients at 0. 287. 0.366, and 0.665 lr>mole/hr-ft -atm, respectively. These results are summarized in Table V. By selecting the limestone grind, one could control the absorption in a given process over a range of S0 concentrations. For the finely ground limestone (89%-325 mesh), the absorption at 1300 ppm was about 95%, while the coarse grind (60%-200 mesh) allowed only 75% removal. 8

2


2

Conclusions The mass-transfer coefficients measured with low sulfur coal for both limestone and sodium hydroxide were essentially the same. In a packed tower, limestone will absorb and react with S0 to the same extent as a strong alkali for flue gas concentrations less than 1000 ppm. For both high and low sulfur fuels, the limestone stoichiometric feed allows control of the outlet S0 emission. Packed towers will allow flexible control of the SO2 emission. Mass-transfer for high sulfur coal applications is liquid phase resistant; the contact time and high surface exposure allowed in a packed tower reduces this adverse condition. The limestone grind affects the absorption significantly at S02 concentrations above 1000 ppm. High absorption (95%) can be achieved with an 89%-325 mesh material at 1300 ppm. 2

2

Literature Cited 1. Jimeson, R. M . , Gakner, A., 71st National Meeting, AIChE, February 1972. 2. Environmental Protection Agency, "Background Information for Proposed New-Scource Performance Standards," August 1971. 3. Berkowitz, J. B., 10th Monthly Report, E P A Contract No. 6802-0215. 4. Chilton, T . H . , Coluburn, A. P., Ind. Eng. Chem. (1934 ) 26, 1183. 5. Gleason, R. J., Final Report, E P A Contract No. EHS-D-71-24, October 1971. 6. Gleason, R. J., 2nd International Lime/Limestone-Wet Scrubbing Symposium, New Orleans, November 1971. RECEIVED February 15, 1973.


Limestone Wet Scrubbing of Sulfur Dioxide from Power Generation

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